EP1666504A1 - Wasserverträgliche Energie-härtbare Zusammensetzungen, die Maleimidderivate enthalten - Google Patents

Wasserverträgliche Energie-härtbare Zusammensetzungen, die Maleimidderivate enthalten Download PDF

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EP1666504A1
EP1666504A1 EP06002749A EP06002749A EP1666504A1 EP 1666504 A1 EP1666504 A1 EP 1666504A1 EP 06002749 A EP06002749 A EP 06002749A EP 06002749 A EP06002749 A EP 06002749A EP 1666504 A1 EP1666504 A1 EP 1666504A1
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group
meth
acid
acrylate
ether
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EP1666504B1 (de
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David Anthony Biro
Mikhail Laksin
Yoshinobu Sakurai
Hisatomo Yonehara
Katsuji Takahashi
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DIC Corp
Sun Chemical Corp
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Dainippon Ink and Chemicals Co Ltd
Sun Chemical Corp
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Priority claimed from EP19980960209 external-priority patent/EP1073685B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing imide group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention relates to active water compatible energy curable compositions containing a maleimide derivative, useful for preparing various coatings, printing inks, surface finishes, moldings, laminated plates, adhesives, and binders. More specifically, the present invention relates to an active water compatible energy curable compositions which can be cured in the absence of a photoinitiator with a irradiation source of practical intensity and energy value.
  • An active energy curable composition polymerized under irradiation of active energy such as thermal energy, ultraviolet light, visible light, and the like, has an advantage of being rapidly cured.
  • Active energy curable compositions are widely used as paints, inks, adhesives, coatings, and the like.
  • conventional ultraviolet active energy curable compositions cannot initiate polymerization alone upon irradiation with an energy source; it is therefore necessary to use a photoinitiator.
  • photoinitiators are used in large quantities, curing progresses rapidly which encourages the use of large quantities of photoinitiator.
  • Photoinitiator compounds having an aromatic ring are used in general because they effectively absorb ultraviolet light. However, these compounds cause problems such as the yellowing of the cured materials upon addition of heat or light. Moreover, low molecular weight energy curable monomers and oligomers, commonly used as photoinitiators because of their solubility a property necessary to initiate photopolymerization effectively, unfortunately have high vapor pressures. Therefore, they tend to give off unpleasant odors at temperatures ranging from room temperature to 150°C. Because infrared light, for example, is generated from an ultraviolet energy source, active energy curable compositions are heated substantially upon contact with such light sources. The heating problem is magnified when the ultraviolet light lamps are arranged and used in a side by side fashion. The unpleasant odors given off from the photoinitiator result in an unhealthy working environment.
  • Unreacted or decomposed photoinitiators remain behind in conventional energy curable compositions even after exposure to irradiation by the active energy cure source. These unreacted or decomposed photoinitiators cause problems such as changing the color of the cured film to yellow, unpleasant odors, and the like, when the cured film is exposed to heat or light. For example, when a material at high temperature, such as a thermal head, contacts an active energy curable composition comprising photoinitiator, strong unpleasant odors are given off. Finally, when these cured compositions are contacted by water after irradiation, unreacted photoinitiator is exuded; therefore causing the active energy curable composition to be unsuitable for food packaging applications.
  • JP-A-58-89609 discloses an energy curable resin comprising a polymer with polymerizable unsaturated acrylic group and an organic solvent-soluble styrene containing an acrylic thermoplastic resin that does not need a photoinitiator.
  • WO 89/05827 teaches photopolymerizable adhesive compositions comprising a copolymer of methacrylate monomer and/or methyl acrylate and a photopolymerizable monomer. These photocurable compositions, however, cannot be sufficiently cross-linked by practical irradiation energy sources.
  • U.S. Patent 5,446,073 and Polymer Preprints, Vol. 37, No. 2, pp. 348-49, 1996 disclose a photopolymerizing method in which maleimide type materials are mixed with vinyl ethers and acrylates to produce a tough film.
  • the polymerization mechanism involves a charge-transfer complex which is formed by an electron acceptor and an electron donor.
  • many of the maleimides are solid and are hardly dissolved in acrylates.
  • maleimide derivatives can be polymerized in the absence of photoinitiators under irradiation by ultraviolet light.
  • Japanese Patent Applications JP-A-61-250064, JP-A-62-64813, and JP-A-62-79243 teach active energy curable compositions comprising maleimide derivatives such as alkylmaleimides and arylmaleimides.
  • these maleimide derivatives show low photoinitiator properties, therefore making it necessary to use substantial amounts of photoinitiator in the maleimide compositions.
  • U.S. Patent 3,920,618 and Japanese Patent Applications JP-A-50-123138 and JP-A-51-47940 disclose photopolymerizable polymers having an ⁇ -aryl substituted maleimide group at a side chain. It is well known that these pendant type maleimides can be crosslinkable by ultraviolet irradiation (i.e. 2+2 photocycloaddition reaction).
  • U.S. Patent 4,079,041 and Europe Patent 21019 teach polymers having side chain type maleimide groups with alkyl substituents. However, these pendant type maleimides cannot be used to form linear polymers by photopolymerization. Therefore, they are most commonly used to prepare negative printing plates. In addition, the photocrosslinking dimerization reaction takes a rather long time (several tens seconds to several minutes) even with an excess amount of irradiation energy.
  • photocurable compositions comprising maleimide derivatives as electron acceptors and vinyl ethers as electron donors.
  • the photopolymerizable compositions 1,4-bis(vinyloxymethyl)cyclohexane and N-cyclohexylmaleimide or 4-hydroxybutyl vinyl ether and N-(hydroxyalkyl)maleimide, illustrated in these documents are polymerized upon ultra violet irradiation in the absence of a photoinitiator. However, hardening of the coated films does not occur; i.e. the coated films maintain liquid states after ultraviolet irradiation.
  • WO 98/07759 describes energy curable compositions wherein water soluble maleimides are copolymerized with acrylates in the absence of water to produce a cured film.
  • Another object of the present invention is to provide an active water compatible energy curable composition which can be photopolymerized by an energy source of practical intensity and energy value and results in coatings that exhibit cure rates, gloss, hardness and solvent resistance values comparable to those of conventional energy cure systems employing photoinitiators.
  • the present invention is an active water curable energy curable composition
  • a water compatible compound water and a maleimide derivative represented by the Formula (1): wherein n and m each independently represent an integer of 1 to 5, and the sum of m and n is 6 or smaller; R 11 and R 12 each independently represent a linking group selected from the group consisting of a straight or branched chain alkylene group, an alicyclic group, an arylalkylene group, and a cycloalkylalkyene group.
  • the arylalkylene group and the cycloalkyl alkylene group may have an aryl or cycloalkyl group as a main chain or a branched chain, respectively;
  • G 1 and G 2 each independently represent an ester linkage represented by -COO- or -OCO- and;
  • R 2 represents a linking chain having an average molecular weight of 100 to 100,000 selected from the group consisting of (poly)ether and (poly)ester linking chains, in which at least one group consists of a group or groups selected from a straight or branched chain alkylene group, an alkylene group having a hydroxyl group, an alicyclic group, an aryl group, and an arylalkylene group; and connected via at least one linkage selected from the group consisting of an ether and an ester linkage.
  • the active water curable energy curable compositions of the present invention contain a maleimide derivative of Formula 1 mentioned above.
  • R 11 and R 12 of Formula 1 examples of R 11 and R 12 suitable for use in the present invention include straight alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, and the like; alkylene groups having a branched alkyl group such as 1-methylethylene group, 1-methyl-trimethylene group, 2-methyl-trimethylene group, 1-methyl-tetramethylene group, 2-methyl-tetramethylene group, 1-methyl-pentamethylene group, 2-methyl-pentamethylene group, 3-methyl-pentamethylene group, neopentyl group, and the like; alicyclic groups such as cyclopentylene group, cyclohexylene group,
  • the gel fraction is the percentage of material remaining after a cured film has been refluxed, for example, in methyl ethyl ketone for 3 hours at 80°C, then dried at 100°C for one hour.
  • a cured malemide derivative or composition which has a 99.8% gel fraction indicates that only 0.2% of the matrix was solubilized by the above reflux conditions. (i.e. a high degree of conversion).
  • the percentage conversion is defined as the ratio of functional groups to a crosslinked matrix monitored by the disappearance of an IR absorption band during the course of irradiation. This real time IR measurment allows one to quantify percent conversion and provides insight into the reactivity the composition during irradiation.
  • Figures 1 and 2 show a plot of the percent conversion of maleimide to polymerized maleimide material over time as measured by real time infra red analysis
  • Figure 1 shows a plot of real time IR data for a bismalemide derivative (structure shown) where R 2 is polytetramethylene glycol.
  • R 2 is polytetramethylene glycol.
  • the conversion rate becomes lower.
  • the molecular weight of R 2 (curve 6) is less than 100, the real time IR data shows the rate of conversion to be sluggish.
  • Figure 2 shows a plot of real time IR data for a bismalemide derivative (structure shown) where R 2 is polyethylene glycol.
  • R 2 is polyethylene glycol.
  • the conversion rate becomes lower.
  • the molecular weight of R 2 (curves 5 and 6) is less than 100, the real time IR data shows the rate of conversion to be sluggish.
  • the results from Figures 1 and 2 suggest that the average molecular weight of R 2 be more than 100.
  • the average molecular weight of R 2 is more than 100,000, such as in the case of a polyol or a polyester, the raw material for the linking chains is solid in nature and shows poor solubility in common solvents at ambient temperature. Once obtained, these maleimide derivatives are virtually insoluble in common solvents, therefore, making it difficult to obtain a film and cure it. Even if a cured coating film is obtained, the surfaces of the coating shows unevenness. Therefore, it is not suitable that the average molecular weight of R 2 be more than 100,000.
  • R 2 may also be a linkage comprising an oligomer or a polymer containing the above described (poly)ether and (poly)ester groups as repeating units.
  • R 2 suitable for use in the present invention include (poly)ether or a (poly)ester linking chains having an average molecular weight in a range of 100 to 100,000.
  • Linking chains represented by R 2 include: a (poly)ether (poly)ol residue group; a (poly)ester (poly)ol residue group; a (poly)carboxylate ⁇ (poly)ether (poly)ol) ester having a polycarboxylic acid residue group at a terminal end; a (poly)carboxylate ⁇ (poly)ester (poly)ol ⁇ ester having a polycarboxylic acid residue group at a terminal end; and (poly)epoxide forming the linking chains.
  • Linking chains represented by a (poly)ether (poly)ol residue group have an average molecular weight of 100 to 100,000, and comprising a part in which at least one group selected from the group consisting of a straight or branched chain C 2 -C 24 alkylene group; a C 3 -C 24 alicyclic group; and a C 6 -C 24 aryl group, connected with an ether linking chain or a repeating unit thereof.
  • Examples of (poly)ether (poly)ol constructing linking chain include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and the like; modified alkylene glycols in which ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethyolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and the like, are modified by ethylene oxides, propylene oxides, butylene oxides, and tetrahydrofuran.
  • polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and the like
  • modified alkylene glycols are preferable.
  • examples of (poly)ether (poly)ol constructing the above linking chain include hydrocarbon polyols such as a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, a copolymer of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, and the like; polyhydric alcohol compounds such as polytetramethylene hexaglycerin ether (modified hexaglycerin by tetrahydrofuran), and the like.
  • hydrocarbon polyols such as a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, a copolymer of ethylene glycol and tetra
  • Linking chains represented by a (poly)ester (poly)ol residue group have an average molecular weight of 100 to 100,000, and comprising a part in which at least one group selected from the group consisting of a straight or branched chain C 2 -C 24 alkylene group; a C 3 -C 24 alicyclic group; and a C 6 -C 24 aryl group; connected with an ester linking chain or a repeating unit thereof.
  • Examples of (poly)ester (poly)ol constructing the linking chain include (poly)alkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, ethylene glycol, propane diol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexane diol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and the like which are modified by ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and methylvalerolactone; aliphatic polyester polyols which are synthesized by esterification of aliphatic dicarboxylic acids such as adipic acid, dimeric acid, and the like with polyols such as n
  • Examples of (poly)carboxylate ⁇ (poly)ether (poly)ol ⁇ ester having polycarboxylic acid at a terminal, which forms the linking chain include (poly)carboxylate ⁇ (poly)ether (poly)ol ⁇ esters having polycarboxylic acid at a terminal end which are obtained by esterification of polycarboxylic acids such as succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconic acid, sebacic acid, maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, citric acid, tetrahydrofurantetracarboxylic acid, cyclohexanetricarboxylic acid, and the like with (poly)ether(poly)ols disclosed in the above, and the like
  • Examples of (poly)carboxylate ⁇ (poly)ester (poly)ol ⁇ ester having polycarboxylic acid at a terminal, which forms the linking chain include (poly)carboxylate ⁇ (poly)ester (poly)ol ⁇ ester having polycarboxylic acid at a terminal end which is obtained by esterification of polycarboxylic acids such as succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconic acid, sebacic acid, maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, citric acid, tetrahydrofurantetracarboxylic acid, cyclohexanetricarboxylic acid, and the like with (poly)ester(poly)ols disclosed in the above,
  • Linking chains obtained by ring-open reaction of polyepoxides having an average molecular weight of 100 to 100,000, and comprising a part in which at least one group selected from the group consisting of a straight or branched chain C 2 -C 24 alkylene group; a C 3 -C 24 alicyclic group; and a C 6 -C 24 aryl group; connected with an ether linking chain, or a repeating unit comprising the parts, and the like.
  • these linking chains there are no particular limitations placed on these linking chains.
  • Examples of (poly)epoxide forming the linking chain include epichlorohydrin-modified bisphenol type epoxy resin synthesized by the reaction of (methyl)epichlorohydrin with bisphenol A, bisphenol F, modified ethylene oxide thereof, modified propylene oxide thereof; epichlorohydrin-modified hydrogenated hydrogenated bisphenol type epoxy resin synthesized by the reaction of (methyl)epichlorohydrin with hydrogenated bisphenol A and hydrogenated bisphenol F, and by the reaction of ethylene oxide-modified or propylene oxide-modified hydrogenated bisphenol A and bisphenol F; epoxy novolak resin; compounds obtained from the reaction of phenol, bisphenol, and the like with (methyl)epichlorohydrin; aromatic epoxy resin such as glycidyl ester of terephthalic acid, isophthalic acid, pyromellitic acid, and the like; polyglycidyl ethers synthesized from glycols such as (poly)ethylene glycol, (poly)propylene glycol,
  • linking chains R 2 represents, preferred are (poly)ether and (poly) ester linking chains having an average molecular weight of 100 to 100,000 and comprising a repeating unit containing a C 2 -C 24 straight chain or branched alkylene, a C 2 -C 24 alkylene group having a hydroxyl group, and/or a C 6 -C 24 aryl group.
  • the maleimide derivatives represented by Formula (1) used for an active energy curable composition of the present invention can be synthesized by well known techniques from the reaction of, for example, a maleimide compound having a carboxyl group with a compound reactable with the carboxyl groups or from the reaction of a maleimide compound having a hydroxyl group with a compound having a carboxyl group.
  • a maleimide compound having a carboxyl group can be synthesized by well known techniques from the reaction of maleic anhydride with a primary amino carboxylic acid, represented by the following reaction formula. (for example, see D.H. Rich, et al., Journal of Medical Chemistry, Vol. 18, pp. 1004-10, 1975).
  • Examples of a primary amino carboxylic acid suitable for use in such synthesis include asparagine, alanine, ⁇ -alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, ⁇ -methylphenylalanine, lysine, leucine, cycloleucine, 3-aminopropionic acid, ⁇ -aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-aminocaprylic acid, 2-aminononanoic acid, 4-aminononanoic acid, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocapric acid, 10-aminocapric
  • Examples of compounds reactive with the carboxyl groups include polyols or polyepoxides having 2 to 6 functional groups and an average molecular weight of 100 to 100,000 comprising a part or a repeating unit in which at least one linking group selected from the group consisting of a straight chain alkylene group, a branched alkylene group, an alicyclic group, and an aryl group is linked with an ether bond and/or an ester bond.
  • maleimide derivatives represented by Formula (1) can be synthesized in a well-known manner disclosed in Organic Synthesis Collective Volume (C.E. Rehberg, et. al., Vol. 3, pp. 46, 1955). It is preferable, however, that the reaction be carried out under ambient or reduced pressure, and a temperature ranging from room temperature to 150 °C, while dehydrating and using a catalyst.
  • the catalyst examples include acid catalysts such as sulfuric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, strong acidic cation-exchange resin, and the like.
  • the amount of catalyst used should be within a range of 0.01 to 10 wt. % based on the total weight of raw materials.
  • an azeotropic organic solvent with water is also used as a solvent in the reaction. Examples of the azeotropic organic solvent with water include toluene, benzene, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether, and the like.
  • maleimide compounds having a carboxyl group with polyepoxides which are one of the reactive compound with the carboxyl groups.
  • maleimide derivatives represented by Formula (1) can be synthesized in a well-known manner disclosed in Japanese Patent Application JP-A-4-228529. It is preferable, however, that the reaction be carried out at a temperature in a range of room temperature to 150 °C, using a catalyst.
  • the catalyst examples include imidazoles such as 2-methyimidazole and the like; quaternary ammonium salts such as tetramethyl ammonium chloride, trimethylbenzyl ammonium chloride, tetramethyl ammonium bromide, and the like; amines such as trimethylamine, triethylamine, benzylmethylamine, tributylamine, and the like; phosphines such as triphenylphosphine, tricyclohexylphosphine, and the like; laurates such as dibutyltin laurate, and the like; basic alkali metal salts such as potassium acetate, potassium tertiary phosphate, sodium acrylate, sodium methacrylate, and the like; alkali alcoholates such as sodium methylate, potassium ethylate, and the like; anion-exchange resins; and the like.
  • the amount of catalyst should be within a range of 10 to 10,000 ppm based on the
  • an organic solvent which does not comprise a reactive hydrogen may also be used as a solvent in the reaction.
  • organic solvent which does not comprise a reactive hydrogen include aromatic hydrocarbons such as toluene, ethylbenzene, tetralin, cumene, xylene, and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; esters such as formate, methyl acetate, ethyl acetate, n-butyl acetate, and the like; and the like.
  • polyols used as a compound reactive with the carboxyl groups include, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and the like; modified alkylene glycols modified of alkylene glycols such as ethylene glycol, propanediol, propylene glycol, butanediol, butylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, and the like by ethyleneoxide, propyleneoxide, butyleneoxide, tetrahydrofuran, ⁇ -caprolactone, ⁇ -butylolactone, ⁇ -valerolactone, and methylvalerolactone; aliphatic polyols such as
  • polyepoxides used as the compound reactive with the carboxyl groups include, for example, bisphenol type epoxy resins modified by epichlorohydrin, which are synthesized by (methyl)epichlorohydrin with bisphenol A, and bisphenol F, and their modified compounds by ethyleneoxide, propyreneoxide, and the like; hydrogenated bisphenol type epoxy resins and epoxy Novolak® resins (Novolak is a Registered Trademark of Shell Company, Houston, TX) modified by epichlorhydrin which are synthesized by (methyl)epichlorohydrin with hydrogenated bisphenol A, hydrogenated bisphenol F, and their modified compounds by ethyleneoxide, propyleneoxides, and the like; reaction products of (methyl)epichlorohydrin with phenol and biphenol; aromatic epoxy resins such as glycidyl esters of terephthalic acid, isophthalic acid, and pyrrolitic acid; polyglycidyl ethers of glycols such as (poly)ethylene glycol
  • the maleimide derivatives represented by Formula (1) used for an active energy curable composition of the present invention can also be synthesized by the reaction of a maleimide compound having a hydroxyl group with a compound having a carboxyl group.
  • a maleimide compound having a hydroxyl group can be synthesized by maleimide and formaldehyde, represented by the reaction: or by a well-known technique using maleic anhydride and a primary amino alcohol represented by the reaction: (for a detailed synthesis example, see U.S. Patent No. 2526517 and Japanese Patent Application JP-A-2-268155).
  • Examples of a primary amino alcohol include 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-3-phenyl-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-3-methyl-1-butanol, 2-amino-4-methylthio-1-butanol, 2-amino-1-pentanol, 5-amino-1-pentanol, (1-aminocyclopentane)methanol, 6-amino-1-hexanol, 2-amino-1-hexanol, 7-amino-1-heptanol, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanol amine, 4-amino-1-piperazine ethanol, 2-amino-1-phenylethanol, 2-amino-3-phenyl-1
  • Examples of compounds reactive with the hydroxyl groups include polycarboxylic acid having ether bonds and/or ester bonds in one molecule, and an average molecular weight of 100 to 100,000, and comprising a part or a repeating unit in which at least one linking group selected from the group consisting of a straight chain alkylene group, a branched alkylene group, an alicyclic group, and an aryl group; linked with an ether bond and/or an ester bond.
  • maleimide derivatives represented by Formula (1) can be synthesized in a well-known manner disclosed in Organic Synthesis Collective Volume (C.E. Rehberg, et al ., Vol. 3, pp. 46, 1955). It is preferable, however, that the reaction be carried out under ambient or reduced pressure, at a temperature ranging from room temperature to 150 °C, while dehydrating and using a catalyst.
  • the catalyst examples include acid catalysts such as sulfuric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, strong acidic cation-exchange resin, and the like.
  • the amount of catalyst should be within a range of 0.01 to 10 wt. % based on the total weight of raw materials.
  • organic solvents which are azeotropic with water.
  • organic solvents are toluene, benzene, butyl acetate, ethyl acetate, diisopropyl ether, and dibutyl ether, and the like.
  • the radical polymerization inhibitors include, for example, phenol derivatives such as hydroquinone, tert-butylhydroquinone, methoquinone, 2, 4-dimethyl-6-tert-butylphenol, catecol, tert-butylcatecol, and the like; amines such as phenothiazine, p-phenylenediamine, diphenylamine and the like; copper complexes such as copper-dimethyldithiocarbamate, copper-diethyldithiocarbamate, copper-dibutyldithiocarbamate, and the like. These inhibitors may be used alone or in combinations of two or more. It is preferable to select an amount of the inhibitors within a range of 10 to 10,000 ppm against total weight of raw materials.
  • polycarboxylic acids as the compounds, having ether bonds and ester bonds include, for example, but are not limited to, polycarboxylic acids obtained by esterification of dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, and dicarboxylic acid described above with polyols described above, and represented by formula: HOOC ⁇ X'-COO ⁇ Y'( ⁇ OOC ⁇ X' ⁇ COOH) n wherein X' represents residual dicarboxyl groups, Y' represents residual polyol groups, and n is an integer from 1 to 5.
  • dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, succinic acid, he
  • the maleimide derivatives represented by Formula (1) and used for the active energy curable composition of the present invention are obtained by aforementioned preparatory methods, but are not limited to, the methods described herein.
  • a compound which is copolymerizable with the maleimide groups it is possible to add a compound which is copolymerizable with the maleimide groups to be used together in the active energy curable composition containing maleimide derivatives according to the present invention.
  • Practical examples of the compounds which are copolymerizable with the maleimide groups are, for example, compounds having various unsaturated double bonds.
  • Such compounds may include, for example, maleimide derivatives which are not represented by the above Formula (1), (meth)acryloyl derivatives, (meth)acrylamide derivatives, vinyl ester derivatives, vinyl carboxylate derivatives, styrene derivatives, and unsaturated polyesters.
  • maleimide derivatives which are not represented by Formula (1) include, for example, but are not limited to:
  • the (poly)ester (meth)acrylate generally designates (meth)acrylates having at least one ester bond in the main chain; urethane (meth)acrylate generally designates (meth)acrylates having at least one urethane bond in the main chain; the epoxyacrylate generally designates (meth)acrylates obtained by a reaction between (meth)acrylic acid and epoxide with one and more than one functional group; the (poly)ether (meth)acrylate generally designate (meth)acrylates having at least one ether bond in the main chain; the alkyl(meth) acrylate or alkylene(meth)acrylate generally designates (meth)acrylates comprising the main chain formed by a linear alkyl, a branched alkyl, a linear alkylene, or a branched alkylene, and side chains or terminal ends having halogen
  • Examples of the (poly)ester (meth)acrylates which can be used together in the active energy curable composition of the present invention include, for example, but are not limited to, monofunctional (poly)ester(meth)acrylates such as alicyclic-modified neopentylglycol(meth)arylate, caprolactone-modified 2-hydroxyethyl(meth)acrylate, ethyleneoxide- and/or propyleneoxide- modified phthalate(meth)acrylate, ethyleneoxide-modified succinate(meth)acrylate, caprolactone-modified tetrahydrofurfuryl(meth)acrylate; pivalate-esterneopentylglycoldi(meth)acrylate, caprolactone-modified hydroxypivalateesterneopentylglucoldi(meth)acrylate, epichlorohydrine-modified phthalatedi(meth)acrylate; mono-, di-or tri-(meth)acrylates of trio
  • the urethane (meth)acrylate which can be used together in the active energy curable composition of the present invention is a general term representing (meth)acrylates obtained by a reaction between hydroxy compounds having at least one acryloyloxy group and isocyanate compounds.
  • the urethane (meth)acrylate may also be selected from water dilutable aliphatic acrylate or aromatic urethanes.
  • hydroxy compounds having at least one acryloyloxy group include, for example, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, cyclohexanedimethanolmono(meth)acrylate, polyethylene glycol(meth)acrylate, polypropylene glycol(meth)acrylate, trimethylolpropanedi(meth)acrylate, trimethylolethanedi(meth)acrylate, pentaerythritoltri(meth)acrylate or an adduct of (meth)acrylate with glycidyl(meth)acrylate, (meth)acrylate compounds having hydroxyl groups such as 2-hydroxy-3-phenolpropyl(meth)acrylate, and ring-opening reaction products of the above acrylate compounds having hydroxyl groups with ⁇ -caprolact
  • isocyanate compounds include, for example, aromatic diisocyanates such as p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylenediisocyanate, m-xylenediisocyanate, 2, 4-tolylenediisocyanate, 2, 6-tolylenediisocyanate, 4, 4'-diphenylmethanediisocyanate, 3, 3'-dimethyldiphenyl-4, 4'-diisocyanate, 3, 3'-diethyldiphenyl-4, 4'-diisocyanate, and naphthalenediisocyanate; aliphatic or alicyclic diisocyanates such as isophoronediisocyanate, hexamethylenediisocyanate, 4, 4'-dicyclohexylmethanediisocyanate, hydrogenated xylenediisocyanate, norbornenediisocyanate,
  • polyols used to produce polyisocyanates include, for example, (poly)alkylene glycols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)butylene glycol, and (poly)tetramethylene glycol; alkyleneglycols modified by ethyleneoxide, propyleneoxide, butyleneoxide, tetrahydrofuran, ⁇ -caprolactone, ⁇ -butylolactone, ⁇ -valerolactone or methylvalerolactone, such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol; aliphatic polyols such as
  • Epoxy(meth)acrylates capable of being used together in the active energy curable composition of the present invention is a general term for (meth)acrylate obtained by a reaction of epoxides having more than one functional group and (meth)acrylic acids.
  • Epoxides as the raw material of epoxy(meth)acrylate includes, for example, but are not limited to, epichlorhydrin-modified-hydrogenated bisphenol-type epoxy resin, synthesized by (methyl)epichlorohydrin and compounds such as hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, and their modified compounds with ethylene oxide or propylene oxide; alicyclic epoxy resins such as 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclo hexane carboxy- late, bis-(3, 4-epoxycyclohexyl) adipate; alicyclic epoxides such as epoxy resin containing heterocycles such as triglycidylisocyanurate;
  • Poly)ether (meth)acrylates capable of being used together in the active energy curable composition of the present invention include, for example, but are not limited to, aliphatic epoxy acrylates, monofunctional (poly)ether(meth)acrylates such as butoxyethyl(meth)acrylate, butoxytriethylene glycol(meth)acrylate, epichlorohydrin-modified butyl(meth)acrylate, dicyclopentenyloxylethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, ethylcarbitol(meth)acrylate, 2-methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)propylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, phenoxyhydroxypropyl(meth)acrylate, phenoxy(poly)ethylene glycol (meth
  • Alkyl(meth)acrylates or alkylene(meth)acrylates which can be used together in the active energy curable composition of the present invention include, for example, but are not limited to, monofunctional (meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth) acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, pentyl(meth)acrylate, isopentyl (meth)acrylate, neopentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl (meth)acrylate, isooctyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, dodecyl(me
  • (Meth)acrylates having aromatic groups which can be used together in the active energy curable composition of the present invention include, for example, but are not limited to, monofunctional (meth)acrylates such as phenyl(meth)acrylate, benzylacrylate; and di(meth)acrylates such as bisphenol A diacrylate, bisphenol F diacrylate, bisphenol S diacrylate.
  • (Meth)acrylates having alicyclic groups which can be used together in the active energy curable composition of the present invention include, for example, but are not limited to, monofunctional (meth)acrylates having alicyclic structures such as cyclohexyl(meth)acrylate, cyclopentyl(meth)acrylate, cycloheptyl(meth)acrylate, bicycloheptyl(meth)acrylate, isobornyl(meth)acrylate, bicyclopentyldi(meth)acrylate, tricyclodecyl(meth)acrylate, bicyclopentenyl(meth)acrylate, norbornyl(meth)acrylate, bicyclooctyl(meth)acrylate, tricycloheptyl(meth)acrylate, and cholesteroid skeleton-substituted (meth)acrylate; di(meth)acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated
  • poly(meth)acryl(meth)acrylates such as a reaction product of (meth)acrylic acid polymer and glycidyl(meth)acrylate, and a reaction product of glycidyl(meth)acrylate polymer and (meth)acrylic acid; (meth)acrylate having amino groups such as dimethylaminoethyl(meth)acrylate; isocyanul(meth)acrylates such as tris((meth)acryloxyethyl)isocyanurate; phosphagene(meth)acrylate such as hexakis[(meth)acryloyloxyethyl)cyclotriphosphagen]; (meth)acrylate having the skelton of polysiloxane; polybutadiene(meth)acrylate; and
  • (Meth)acrylamide derivatives which can be used together in the active energy curable composition of the present invention include, for example, monofunctional (meth) acrylamides such as N-isopropyl(meth)acrylamide and polyfunctional (meth)acrylamides such as methylenebis (meth)acrylamide.
  • Compounds having vinyl ether groups which can be used together in the active energy curable composition of the present invention can be classified into, but are not limited to, the following groups, in which: an alkyl vinyl ether having a terminal group substituted with at least one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, and an amino group; a cycloalkyl vinyl ether having a terminal group substituted with at least one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, and an amino group; at least one vinyl ether selected from the group consisting of a monovinyl ether, a divinyl ether, and a polyvinyl ether in which a vinyl ether group is connected with alkylene group; and in which a vinyl ether group is connected with at least one group with and without substituent selected from the group consisting of alkyl group, cycloalkyl group, and aromatic group, via at least one linkage
  • Alkylvinyl ethers which can be used together in the active energy curable composition includes, for example, but are not limited to, methyl vinyl ether, hydroxymethyl vinyl ether, chloromethyl vinyl ether, ethyl vinyl ether, 2-hydroxyethylvinylether, 2-chloroethylvinylether, diethyl aminoethyl vinyl ether, propyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-chloropropyl vinyl ether, 3-aminopropyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, 4-hydroxybutyl vinyl ether, isobutyl vinyl ether, 4-aminobutyl vinyl ether, pentyl vinyl ether, isopentyl vinyl ether, hexyl vinyl ether, 1, 6-hexanediol monovinyl ether, heptyl vinyl ether, 2-ethylhexyl vinyl ether
  • Cycloalkyl vinyl ethers which can be used together in the active energy curable composition of the present invention includes, for example, but are not limited to, cyclopropyl vinyl ether, 2-hydroxycyclopropyl vinyl ether, 2-chloro-cyclopropyl vinyl ether, cyclopropylmethyl vinyl ether, cyclobutyl vinyl ether, 3-hydroxycyclobutyl vinyl ether, 3-chlorocyclobutyl vinyl ether, cyclobutylmethyl vinyl ether, cyclopentyl vinyl ether, 3-hydroxycyclopentyl vinyl ether, 3-chlorocyclopentyl vinyl ether, cyclopentylmethyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-aminocyclohexyl vinyl ether, cyclohexanediol monovinyl ether, cyclohexanedimethanol monovinyl
  • the vinyl ether linkage connects with an alkylene group, and at least one group selected from a group consisting of a C 2 -C 24 alkyl group, a C 2 -C 24 alicyclic group and a C 2 -C 24 aromatic group which may have a substituents connects with a linkage selected from a linkage consisting of an ether linkage, an urethane linkage, and an ester linkage
  • examples of the compounds containing an ether linkage for example, but are not limited to, ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methylvinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol methylvinyl ether, triethylene glycol divinyl ether, polyethylene glycol methyl vinyl ether, polyethylene glycol methyl vinyl ether, polyethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl
  • the compounds having urethane linkages may be obtained by the urethanating reaction between a monovinyl ether of (poly)alkylene glycol having at least one hydroxyl group in one molecule and a compound having at least one isocyanate group in one molecule.
  • the monovinyl ether of (poly)alkylene glycol include at least one hydroxyl group in a molecule, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxy-2-methylethyl vinyl ether, dipropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, and 1, 6-hexanediol monovinyl ether.
  • compounds having at least one isocyanate group in one molecule include, for example, aromatic diisocyanates such as m-isopropenyl- ⁇ , ⁇ -dimethylbenzylisocyanate, p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylenediisocyanate, m-xylenediisocyanate, 2, 4-tolylenediisocyanate, 2, 6-tolylenediisocyanate, 4, 4'-diphenylmethanediisocyanate, 3, 3'-diethyldiphenyl-4, 4'-diisocyanate, 3, 3'-dimethyldiphenyl-4, 4'-diisocyanate, naphthalenediisocyanate; and aliphatic and alicyclic isocyanates such as propylisocyanate, isophoronediisocyanate, hexamethylenediisocyanate; and
  • isocyanate compounds such as dimers or trimers comprising more than one of these isocyanate monomers, and to use adduct compounds obtained by urethanating reactions between isocyanate compounds containing more than 2 isocyanate groups in one molecule and various alcohols.
  • alcohols can be used for obtaining adduct products, if the alcohol contains at least one hydroxyl group. Although there is no limitation, it is preferable to use an alcohol with an average molecular weight of less than 100,000.
  • examples of such alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 10-decanediol, 2, 2', 4-trimethyl-1, 3-pentanediol, 3-methyl-1, 5-pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, neopentylg
  • Polyester-polyols obtained by reactions of the above polyol components and carboxylic acids may be used in preparing the adduct products.
  • carboxylic acids any conventional carboxylic acids or anhydrides thereof may be used. Examples of these carboxylic acids include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hettic acid, chrolendick acid, dimeric acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2, 2, 4-trimethyladipic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodiumsulfoterephthalic acid, 2-potassiumsulfoterephthalic acid, isophthalic acid; 5-sodiumsulfoisophthalic acid, 5-potassiumsulfoisophthalic acid; di-lower-alkylesters of 5-
  • polyether polyols conventional polyether polyols can be used in obtaining adduct products.
  • polyether-polyols are, for example, but are not limited to, ether glycols such as polytetramethylene glycol, propylene oxide-modified polytetramethylene glycol, ethylene oxide-modified polytetramethylene glycol, polypropylene glycol, polyethylene glycol, and polyether polyols obtained by ring-opening reactions of cyclic ethers by use of more than three functional polyols as an initiator.
  • Polycarbonate polyols used in adduct products are obtained by the transesterification reactions of carbonates and various polyols.
  • carbonates are, for example, but are not limited to, diphenylcarbonate, bischlorophenylcarbonate, dinaphtylcarbonate, phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate, and 2-tolyl-4-tolyl-carbonate; diaryl- or dialkyl-carbonates such as dimethylcarbonate and diethylcarbonate.
  • polyols which can be used in the above reaction include the alcohols, polyols, polyester polyols, and polyether polyols described above.
  • Compounds having ester linkages classified in vinyl ether groups can be obtained by the esterification reaction of monovinyl ether of alkylene glycol having at least one hydroxyl group in a molecule with a compound having at least one carboxyl group in a molecule.
  • Examples of monovinyl ether of alkylene glycol having at least one hydroxyl group in a molecule are the same compounds as recited as components of the above compounds having urethane bonds.
  • carboxylic acids and anhydride thereof for the compounds having at least one carboxyl group in a molecule.
  • the compound having at least one carboxyl group in a molecule include, for example, but are not limited to, formic acid, acetic acid, propionic acid, valeic acid, benzoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hettic acid, chlorendic acid, dimeric acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2, 2', 4-trimethyladipic acid, 1, 4-cyclohexanedicarboxyl acid, terephthalic acid, 2-sodiumsulfoterephthalic acid, 2-potassiumsulfoterephthalic acid, isophthalic acid, 5-sodium-sulfoisophthalic acid, 5-potassiumsulfo
  • Vinyl carboxylate derivatives which can be used together in the active energy curable compositions include, for example, vinyl acetate and vinyl cinnamate.
  • Styrene derivatives include, for example, styrene and divinylstyrene.
  • Unsaturated polyesters which can be used together in the active energy curable composition include, for example, maleates such as dimethylmaleate and diethylmaleate; fumarates such as dimethylfumarate and diethylfumarate; and esterification products of unsaturated polycarboxylic acids such as maleic acid and fumaric acid and polyhydric alcohols.
  • water compatible is used herein to describe compounds that are partially or substantially water dilutable, water soluble and/or capable of forming a water emulsion or dispersion with the energy curable compositions herein.
  • the particular water compatible compound be compatible with both the water and maleimide deriviatives in order to avoid any phase separation or precipitation of one of more of the components.
  • the water compatible resin compounds used for coating applications work best if the possess functional groups which are compatible with water on one hand and functional groups which are compatible with the maleimide derivatives on the other.
  • maleimide derivatives represented by Formula (1) there is no particular limitation in the ratio of maleimide derivatives represented by Formula (1) to those maleimide derivatives when both maleimide derivatives are used together in the active energy curable composition containing maleimide derivatives, it is preferable to select the ratio of maleimide derivative other than these represented by Formula (1) equal or less than 95% by weight and more preferably equal or less than 90% by weight.
  • the ratio of a compound having acryloyloxy or methacryloyloxy groups to the maleimide derivatives represented by Formula (1) when used in the active energy curable composition of the present invention containing maleimide derivatives, it is preferable to use the compound having acryloyloxy or methacryloyloxy groups such that 100 parts by weight of the compounds having acryloyloxy or methacryloyloxy groups constitutes a ratio of equal or more than 5 parts by weight of maleimide derivatives represented by Formula (1), and, more preferably, the ratio of equal or more than 20 parts by weight from the point of view of the curing speed.
  • the ratio to be incorporated in the composition there is no limitation on the ratio to be incorporated in the composition.
  • the active energy curable compositions of the present invention have an intrinsic spectral sensitivity ranging from 200 to 400 nm, and it is possible to polymerize same under a irradiation of ultraviolet or visible light within a range of 180 to 500 nm, even without use of a photoinitiator. It was observed that lights having wavelengths at 254 nm, 308 nm, 313 nm, and 365 nm are effective in curing of the active energy curable composition of the present invention. It is also possible to cure or polymerize the present active energy curable composition by light other than the ultraviolet light and by heat. In addition, it is possible to cure the present active energy curable composition in air and/or an inert gas.
  • Various energy cure sources such as thermal, ultraviolet light, infrared and visible light may be used, for example, a low-pressure-mercury lamp, a high-pressure-mercury-lamp, an ultrahigh-pressure-mercury lamp, a metal halide lamp, a chemical lamp, a black-light lamp, a mercury-xenon lamp, an excimer lamp, a short-arc lamp, a helium-cadmium laser, an argon laser, an excimer laser, and sunlight.
  • a low-pressure-mercury lamp a high-pressure-mercury-lamp, an ultrahigh-pressure-mercury lamp, a metal halide lamp, a chemical lamp, a black-light lamp, a mercury-xenon lamp, an excimer lamp, a short-arc lamp, a helium-cadmium laser, an argon laser, an excimer laser, and sunlight.
  • a low-pressure-mercury lamp such as thermal, ultraviolet light, infrared
  • the active energy curable compositions of the present invention can be cured under irradiation of ultraviolet light or visible light, in the absence of a photoinitiator, conventional photoinitiators may nonetheless be used for polymerization.
  • the photoinitiators may be classified into two groups; one is an intramolecular-bond-cleavage type and the other is an intramolecular-hydrogen-abstraction type.
  • intramolecular-bond-cleavage type photoinitiators include, for example, acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxylethoxy)phenyl-(2-hydroxy-2-methylpropyl)ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone; benzoins such as benzoin, benzoinmethyl ether, benzoinisopropyl ether; acylphosphine oxides such as 2, 4, 6-trimethylbenzophen
  • intramolecular-hydrogen-abstraction type photoinitiators include, for example, benzophenones such as benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4, 4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylic-benzophenone, 3, 3', 4, 4'-tetra(t-butylperoxycarbonyl)benzophenone, 3, 3'-dimethyl-4-methoxybenzophenone; thioxanthones such as 2-isopropyl-thioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethyl-thioxanthone, 2, 4-dichlorothioxanthone; aminobenzophenones such as Michler's ketone, 4, 4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone
  • the photoinitiator to the active energy curable composition within a range of 0.01 to 10.00% by weight.
  • the active energy curable compositions of the present invention can be cured by irradiation of ultaviolet, it is also possible to use a sensitizer for efficient curing.
  • sensitizers are, for example, amines such as triethanolamine, methyldiethanolamine, triisopropano-lamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethyl-aminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethyl-amino)ethyl benzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate. It is preferable to add the sensitizer to the active energy curable composition within a range of 0.01 to 10.00% by weight.
  • additives such as non-reactive-compounds, inorganic fillers, organic fillers, coupling reagents, adhesive reagents, antifoaming reagents, leveling reagents, plasticizers, antioxidants, ultraviolet-absorbers, flame retardants, pigments, dyes, and paints.
  • liquid or solid oligomers or resins with a low reactivity or non- reactivities such as, alkyl (meth)acrylate copolymer, epoxy resins, liquid polybutadiene, liquid poly
  • Inorganic and organic fillers are generally used for improving mechanical properties such as strength, cushioning and slipping properties.
  • Inorganic fillers which may be used include, for example, but are not limited to, silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaoline clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica spherules, and glass spherules.
  • halogen groups, epoxy groups, hydroxyl groups, and thiol groups are added to these fillers by addition or by the reaction with various coupling reagents such as a silane coupling reagent, a titanate-type coupling reagent, an aluminum-type coupling reagent, a zirconate-type coupling reagent, and the like.
  • various coupling reagents such as a silane coupling reagent, a titanate-type coupling reagent, an aluminum-type coupling reagent, a zirconate-type coupling reagent, and the like.
  • organic fillers which may be used include, for example, but are not limited to, a benzoguanamine resin, a silicone resin, a low-density polyethylene, a high-density polyethylene, a polyolefin resin, ethylene-acrylate copolymer, polystyrene, cross-linking polystyrene, polydivinylbenzene, styrene-divinylbenzene copolymer, acrylic copolymer, cross-linking acrylic resin, polymethylmethacrylate resin, vinylidene-chloride resin, fluororesin, nylon 12, nylon 11, nylon 6/66, phenolic resin, epoxy resin, urethane resin, and polyimide resin. It is possible to add halogen groups, epoxy groups, hydroxyl groups, and thiol groups to these organic fillers.
  • Examples of coupling reagents which can be used together in the active energy curable composition of the present invention include, for example, but are not limited to, silane coupling reagents such as ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -chloropropyltrimethoxysilane; titanate coupling reagents such as tetra(2, 2-diaryloxymethyl-1-butyl)bis(ditridecyl) phosphitetitanate, and bis(dioctylpyrophate) ethylenetitanate; aluminum coupling reagents such as acetoalkoxyaluminumdiiospropylate; zirconium coupling agents such as acethylacetone-zirconium complex and the like.
  • silane coupling reagents such as ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -chloropropyltrimethoxysilane
  • any corresponding conventional additives may be used together, without any limitation, in the active energy curable composition of the present invention, if the additives are compatible with the water containing composition and do not harm the characteristics of the resin including the curing property.
  • the aforementioned components may be mixed, the mixing order or mixing method are not limited.
  • solvents including ketones such as methylethylketone and methylisobutylketone; acetates such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; and alcohols such as methanol, ethanol, isopropyl alcohol, butanol; and water.
  • the active energy curable composition of the present invention is advantageously applicable for surface finishing, binders, plastic materials, molding materials, laminate plates, adhesives, bonding materials, and ink; coating materials for metals such as aluminum, iron, and copper; coating materials for plastics such as vinyl chloride, acryls, polycarbonate, polyethyleneterephthalate, and a acrylonitrilbutadienestyrene copolymer, polyethylene, and polypropylene; coating materials for ceramics such as glass; coating materials for other materials such as wood, paper, printing papers, and fibers.
  • the active energy curable composition of the present invention forms a cured film without a photoinitiator under irradiation of light. Since this active energy curable composition of the present invention does not generate odor during curing, and the cured film of this composition does not incur yellowing and odor, and an amount of elution from this cured film is quite low, the present composition can be advantageously applied to a field of inks such as lithographic ink, flexo-ink, gravure ink, and screen ink, and to fields of gloss varnish, paper coating, wood painting, beverage can coating, printing, soft package coating, adhesives for printed papers and laminates, lavel coating, printing ink or adhesives, thermosensible paper, printing ink or coating for thermosensible paper, food package coating, printing ink, adhesives, and binders, which are directly contacted with a consumer.
  • inks such as lithographic ink, flexo-ink, gravure ink, and screen ink
  • the energy curable compositions were coated on opacity charts (uncoated Leneta N2A, available from Leneta Corporation, Mawah, NJ) using a #3 Mayer rod having a thickness of 7.5 microns.
  • the ultraviolet radiation energy cure source was provided using a conveyor type unit with a medium pressure mercury lamp of variable light intensities (e.g. 120, 200, 300 watts per inch (wpi) available from Fusion Aetek, Rockville, MD) at conveyor speeds varying from 100 to 200 feet per minute (fpm). At 200 wpi and 100 fpm the ultraviolet exposure dose was 228 mJ/cm 2 , measured using a radiometer (UV Power Puck® , Power Puck is Registered Trademark of EIT Incorporated, VA).
  • This dose is normally sufficient to produce a commercially viable film.
  • the surface hardness of the coating was empirically measured by scratching the surface with a human nail.
  • the reflective gloss of the cured film was measured at 60° using a glossmeter (Micro-Gloss 60, available from BYK-Gardner Incorporated, MD).
  • the solvent resistance of the cured film was measured by the surface with a cotton tipped applicator soaked in methyl ethyl ketone (MEK), isopropyl alcohol or water until the substrate was exposed. The number of rubs, i.e. one stroke back and forth across a surface, were recorded. A coating exhibiting 10 rub MEK resistance, for example, was considered to be commercially feasible.
  • the residue obtained by removing toluene from the reaction mixture, was acidified to a pH of 2 with 0.1 N HCl, extracted 3 times with ethyl acetate (100 ml) and dried with magnesium sulfate. The ethyl acetate was then evaporated under reduced pressure and the residue was recrystallized from water, whereby pale yellow crystals of maleimidoacetic acid (11 g) were obtained.
  • Maleimidoacetic acid (6.8 g), polytetramethylene glycol (10 g, MW of 250, tradename PolyTHF 250, available from BASF Corporatioin, Japan), p-toluenesulfonic acid (1.2 g), 2, 6-tert-butyl-p-cresol (0.06 g), and toluene (15 ml) were added together and reacted at 80 °C for 4 hours under reduced pressure (240 torr). The mixture was stirred and the water formed during the reaction was removed.
  • reaction mixture was then dissolved in toluene (200 ml) and washed 3 times with a saturated sodium hydrogen carbonate aqueous solution (100 ml) and a saturated sodium chloride aqueous solution (100 ml).
  • the toluene was then removed under reduced pressure and a maleimide derivative (16 g) having the structure below was obtained.
  • the residue obtained by removing toluene from the reaction mixture, was acidified to a pH of 2 with 0.1 N HCl, extracted 3 times with ethyl acetate (100 ml) and dried with magnesium sulfate. The ethyl acetate was then evaporated under reduced pressure and the residue was recrystallized from water, whereby pale yellow crystals of maleimidoacetic acid (11 g) were obtained.
  • Maleimidoacetic acid (6.8 g), pentaerythritol modified by 4 moles of ethalene oxide (4.1 g, tradename PNT-40 Mn:490, Mw:530, available from Nippon Emulsifying Agent Co., Ltd., Japan), p-toluenesulfonic acid (1.2 g), 2, 6-tert-butyl-p-cresol (0.06 g), and toluene (15 ml) were added together and reacted at 80 °C for 4 hours under reduced pressure (240 torr). The mixture was stirred and the water formed during the reaction was removed.
  • ethalene oxide 4.1 g
  • PNT-40 Mn:490, Mw:530 available from Nippon Emulsifying Agent Co., Ltd., Japan
  • p-toluenesulfonic acid 1.2 g
  • 2, 6-tert-butyl-p-cresol (0.06 g)
  • toluene 15 m
  • reaction mixture was then dissolved in toluene (200 ml) and washed 3 times with a saturated sodium hydrogen carbonate aqueous solution (100 ml) and a saturated sodium chloride aqueous solution (100 ml).
  • the toluene was then removed under reduced pressure and a maleimide derivative (18 g) having the structure below was obtained.
  • the maleimide prepared in Example 1 (36 wt. %, MIA250, available from DaiNippon Ink and Chemical Corporation, Tokyo, Japan) was to water (15 wt.%).
  • a polyether siloxane additive (0.5 wt. %, Glide 440, available from Tego Chemie, VA) was then added to produce sufficient flow properties. The energy curing properties of the coating could not be evaluated because the water and maleimide were found to be incompatible and no film was produced.
  • a water dilutable aliphatic urethane acrylic resin (25 wt.%, Ebecryl 2001, avialable from UCB Radcure, GA) was combined with water (49.5 wt.%).
  • the maleimide prepared in Example 1 (25 wt. %, MIA250, available from DaiNippon Ink and Chemical Corporation, Tokyo, Japan) was added along with a polyether siloxane additive (0.5 wt. %, Glide 440 available from Tego Chemie, VA) to produce sufficient flow properties.
  • the composition was irradiated at two different doses. The curing, solvent resistance, gloss and surface hardness properties of the coating described above were then evaluated. The results are shown in Table 1.
  • a highly alkoxylated trimethylolpropane triacrylate resin (61 wt.%, SR 9035, available from Sartomer, PA) was combined with water (24 wt.%).
  • the maleimide prepared in Example 1 (14.5 wt. %, MIA250, available from DaiNippon Ink and Chemical Corporation, Tokyo, Japan) was added.
  • a polyether siloxane additive (0.5 wt. %, Glide 440, available from Tego Chemie, VA) was then added to produce sufficient flow properties.
  • the composition was irradiated at two different doses. The curing, solvent resistance, gloss and surface hardness properties of the coating described above were then evaluated. The results are shown in Table 1.
  • a vinyl ether, hexanedioic acid, bis[4-ethenyloxy) butyl]ester (67 wt.%, VEX 4060, available from Allied Signal, NJ) was added to water (22 wt.%).
  • the maleimide prepared in Example 1 (21.5 wt. %, MIA250, available from DaiNippon Ink and Chemical Corporation, Tokyo, Japan) was added along with a polyether siloxane additive (0.5 wt. %, DC57, available from Dow Chemical, Midland, MI) to produce sufficient flow properties.
  • the energy curing properties of the coating could not be evaluated because the water and malemide were found to be incompatible and no film was formed.
  • a maleimide prepared in Example 2 (84.5 wt. %, MIA-PE4EO, available from DaiNippon Ink and Chemical Corporation, Tokyo, Japan) was added to water (15 wt.%).
  • a polyether siloxane additive (0.5 wt. %, Glide 440, available from Tego Chemie, VA) was then added to produce sufficient flow properties. The energy curing properties of the coating could not be evaluated because the water and maleimide were found to be incompatible and no film was produced.
  • Table 1 shows several characteristics of the water compatible energy curable compositions of the present invention.
  • the dose required to cure the composition was similar to that used to cure conventional energy curable materials.
  • the surface hardness and gloss of the cured films were comparable to commercial coatings using photoinitiators.
  • the solvent rubs of the cured compositions were typical of the results that would be achieved with a similar composition containing commercial photoinitiators and resins. This is by exemplified by Example 3 wherein the cure rate does of 228 mJ/cm 2 represents a conveyor speed of 100 fpm and 200 wpi lamp intensity, represent a commercially practical amount of energy delivered to cure the composition. Examples 3 and 7 depict gloss values greater than 80 which are indicative of a high commercial grade gloss.
  • Example 3 depicts solvent rubs of 65 with MEK and greater than 200 with water. These values are typically higher than those shown for conventional commercial coatings cured under similar conditions.
  • Example 6 shows that by doubling the curing dose, from 125 to 254 mJ/cm 2 , for the energy curable compositions of the present invention, one can improve its film properties, such as surface hardness, gloss and crosslink density as measured by solvent resistance and illustrated by an increase in MEK solvent rubs from 8 to 38.
  • Example 9 shows a similar increase in solvent rubs, from 9 to 31 MEK rubs and 31 to 66 water rubs. Although a higher cure rate dose was required, it was still within the range for commercial curing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP06002749A 1998-11-14 1998-11-14 Verwendung von Maleimidderivaten in wasserverträglichen Energie-härtbaren Zusammensetzungen Expired - Lifetime EP1666504B1 (de)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012176915A1 (en) * 2011-06-24 2012-12-27 Fujifilm Corporation Ink composition, image forming method and printed material
WO2013083956A1 (en) * 2011-12-08 2013-06-13 Sericol Limited Radiation curable inks
US8921443B2 (en) 2010-08-18 2014-12-30 Henkel IP & Holding GmbH Radiation curable temporary laminating adhesive for use in high temperature applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170015856A1 (en) * 2014-03-28 2017-01-19 Sun Chemical Corporation Low migration radiation curable inks

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675414A (en) * 1985-03-08 1987-06-23 The United States Of America As Represented By The Secretary Of The Navy Maleimidomethyl-carbonate polyethers
US4745197A (en) * 1986-07-02 1988-05-17 Basf Aktiengesellschaft Flexible bismaleimides
WO1998011152A1 (fr) * 1996-09-12 1998-03-19 Cray Valley S.A. Compositions de revetement polymerisables et/ou reticulables par la lumiere ultraviolette ou visible
EP0878482A1 (de) * 1997-05-16 1998-11-18 Dainippon Ink And Chemicals, Inc. Durch aktive Strahlung härtbare Zusammensetzung aus einem Maleimidderivat und Verfahren zu deren Härtung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675414A (en) * 1985-03-08 1987-06-23 The United States Of America As Represented By The Secretary Of The Navy Maleimidomethyl-carbonate polyethers
US4745197A (en) * 1986-07-02 1988-05-17 Basf Aktiengesellschaft Flexible bismaleimides
WO1998011152A1 (fr) * 1996-09-12 1998-03-19 Cray Valley S.A. Compositions de revetement polymerisables et/ou reticulables par la lumiere ultraviolette ou visible
EP0878482A1 (de) * 1997-05-16 1998-11-18 Dainippon Ink And Chemicals, Inc. Durch aktive Strahlung härtbare Zusammensetzung aus einem Maleimidderivat und Verfahren zu deren Härtung

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8921443B2 (en) 2010-08-18 2014-12-30 Henkel IP & Holding GmbH Radiation curable temporary laminating adhesive for use in high temperature applications
WO2012176915A1 (en) * 2011-06-24 2012-12-27 Fujifilm Corporation Ink composition, image forming method and printed material
JP2013006968A (ja) * 2011-06-24 2013-01-10 Fujifilm Corp インク組成物、画像形成方法及び印画物
US9068095B2 (en) 2011-06-24 2015-06-30 Fujifilm Corporation Ink composition, image forming method and printed material
WO2013083956A1 (en) * 2011-12-08 2013-06-13 Sericol Limited Radiation curable inks
GB2510733A (en) * 2011-12-08 2014-08-13 Sericol Ltd Radiation curable inks
GB2510733B (en) * 2011-12-08 2020-11-18 Sericol Ltd Radiation curable inks

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ATE480571T1 (de) 2010-09-15
EP1666504B1 (de) 2010-09-08
DE69841892D1 (de) 2010-10-21

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